AU627000B2

AU627000B2 - Aqueous resin preparations for consolidating rock and filling cavities and process therefor

Info

Publication number: AU627000B2
Application number: AU51801/90A
Authority: AU
Inventors: Edmund Edel; Claus-Peter Herold; Heinz Muller; Stephan Von Tapavicza
Original assignee: Henkel AG and Co KGaA
Current assignee: E Epple and Co GmbH; BASF Personal Care and Nutrition GmbH
Priority date: 1989-03-11
Filing date: 1990-03-03
Publication date: 1992-08-13
Anticipated expiration: 2010-03-03
Also published as: DE3907989A1; ZA901858B; EP0462151B1; JPH04503982A; WO1990010780A1; NO301429B1; EP0462151A1; ATE109542T1; AU5180190A; CA2049037C; US5199823A; CA2049037A1; NO913571D0; JP2997041B2; DE59006711D1; NO913571L

Abstract

PCT No. PCT/EP90/00353 Sec. 371 Date Nov. 6, 1991 Sec. 102(e) Date Nov. 6, 1991 PCT Filed Mar. 3, 1990 PCT Pub. No. WO90/10780 PCT Pub. Date Sep. 20, 1990.The invention relates to aqueous preparations of acid-catalyzed melamine resins and/or urea-formaldehyde condensates which contain an addition of zeolite NaA and/or hydroxysodalite to increase their usefulness. The preparations in question are particularly suitable for use in the stabilization of rock and/or plugging of cavities, for example in tunneling and mining. Accordingly, the invention also relates to a process for stabilizing rock, for example in tunneling and mining, by injection of corresponding preparations together with an acidic catalyst.

Description

I OPI DATE 09/10/90 APPLN. I D 51801 PCT NUMBER PCT/EP90/00353

PCI?

INTERNATIONALE ANMELDUNG VEROFFENTLICHT NACH DEM VERTRAG UB~r5 DIE INTERNATIONALE ZUSAMMENARBEIT AUF DEM GEBIET DES PATENTWVESENS (PCT) (51) Internatieoale Patcntklassirikation 5 E21B 33/138, C09K 17/00 CObK 3/34 Al (21) Internationales Aktenzeichen: (22) Internationales Anmeldedatum: Priorititsdategi: P 39 07989.9 11 M PCT/EP90/0035 3. Mflrz 1990 (03.03.9 atrz 1989 (It.03.89) (11) In~ternationale Veriiffentlichungsnummer: WO 90/10780 (43) Intern ationales Veriifent.1iehungsdatum: 20. September 1990 (20.09.90) i3 (81) Bestiinmungsstaaten: AT (europilisches Patent), AU, BE (europflisches Patent), CA, CH (europiiisches Patvnt), 0) DE (europflisches Patent), DK (europfiisches Patent), ES (europ~Iisches Patent), FR (europiiisches Patent), GB (europflisches Patent), IT (europdischies Patent), JP, LU (europilisches Patent), NL (europilisches Patent), NO, E SE (europiiisches Patent), US, Ver~iffentlicht N Mit internationalern Recherclhenbericli.

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(71) Anwni;14r Oi~r alle Bestrnungsstaawen ausser US): HE KEL KGMvMANDITGESELLSCHAFT AUF AKTIE IDE/ DkJ -1 klsr~ 67 -4000 Dilsseldorf-Holtiai sen (D1 E, EPPLE CO. Gekltae6,DMBH [DE/DE]; Seiden tra~e 5-57i D-7000 Stuttgart I (DE).

(72) Effinder; undt Erl'inder/Anjnelder ('nur filr US) :MU0,LLER, Heinz [DE DE]; Goldregenweg 4, D-4019 Monheim, HI ROLD, Claus-Peter [DE/DE]; Ostpreu~enktrIe 26, 1 4020 Mettmann VON TAPAVICZA, Stepha [DE/DEJ; Thomas- Mann-S irage 12, D-4000 Erkrath EDEL, Edmund Oberlinstra~e 3, 1 7024 Filderstadt 1 (DE), (54) Title: A\,,'JEOUS RESIN PREP,'RATIONS FOR CONSOLIDATING ROCK AND FILLING CAVITIES AND PRO- CESS THEREFOR (54) Bezeichnung: WASSRIGE PIARZZUBER,,ITUNGEN FOR DIE GESTEINSVERFEST0UNG VNY,. HOHLRAUMty- VERFOLLUNC UND VERFAHREN HIERZU (57) Abstract The use of aqueous preparations of acid-curing malamine resins and/ur urea formaldehyde condensates is facilitated if they contain a zeolite NaA and/or hydrogodalith additive, These preparations are particularly suitable for use in consolidating rock and/or filling cavities, e~g. in tunnelling or mining. In a process for consolidating rock, e~g. in tunnelling or mining, suitable preparations are injected together with an acid hardener, (57) Zusamnienfassung Die Erfindung betrifft wflllige Zuberfitungen von sliurehllrtbaren MAelaininharzen und/oder Harnstoff-Forrnaldehy~z- Kondensaten, dik zur Erh~5huni ihrer Gebrauchisflihigkeit einen Zusatz von Zeolith NaA .nd/oder Hydrosodalith enthalten, Derartige Zubereitungen sind in~sbesondero fOr den Eirsatz bei der Gesteinsvcrfestig~ng und/oder Hohilrauinverfallung zum Beispiel im Tunnel- und Bergbau geeignet. Vieientsprechend hetrifft die Erfindung, ferner emn Verfahrer zur Gesteinsverfestigung zumn Beispiel im Tunnel., und Bergbau durch lnjctition entsprechender Zubereitungen zusammen mit einem sauren Hflrter,

I

Henkel KGaA Dr. FU/ku 8.3.1989 Patent Application D 8609 Aqueous Resin Preparations For Consolidating Rock and Filling Cavities and Process Therefor This invention relates to improvements in aqueous resin systems based on melamine resins and/or urea-formaldehyde resins which are used for stabilizing rock and for plugging cavities.

The improvement L rock strength by injection of auxiliary chemicals typically made up with water is an old and multifarious problem. Various suspensions, emulsions or solutions are available as sealing and stabilizing media. Cement and inorganic sodium silicates are basically inexpensive and economical, but can only be sensibly used where rock permeability is sufficiently high and few, if any, aggressive waters are present. Improved working conditions and strength properties are obtained through the use of organic resins. The resins may be used in the form of solutions and/or suspensions and/or emulsions, considerable possibilities in regard to the modification of strength, vise ity, adhesiveness of the stabilizing material to the rock and the like being afforded by the particular choice of the resins. Various types of resins have been proposed for the purpose in questions, including for example epoxy resins, polyurethanes and other thermoplastics and thermosets.

Today, particular significance is attributed to systems Lased on polyurethanes of the type described, for example, in the journal "Glickauf", 112 (1976), 803-807.

4 ii t a u V

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D 8609 2 On account of the high toxicity of isocyanates, however, these systems are being used increasingly less for ecological reasons.

Melamine- and urea-formaldehyde resins have also been proposed, normally being injected in aqueous solution or suspension into the rock to be cemented where they cure in largely predeterminable times under the effect of a catalyst applied at the same time. The catalysts used for the resins in question are acidic and/ol alkaline systems, particular significance being attributed to the acidic systems and, among these, to the mineral acids. The prior art relating to improvements in rock strength by chemical injections, particularly in connection with the plugging of oil and gas wells, is represented for example by DE-AS 11 53 698 and by the Article by H. Barthel "Verbesserung der Gebirgsfestigkeit durch chemische Injektionen (Improving Rock Strength by Chemical Injections)", Bergb.-Wiss. 17 (1970), No. 8, 281 to 285.

A technological difficulty attending the use of melamine- or urea-formaldehyde systems lies in the instability of aqueous preparations of such resins which, even in the absence of acidic catalysts, undergo a considerable increase in viscosity relatively quickly, so that their processability is impaired. In particular, the injectability and penetrative power of the injected resin solution are increasingly impaired. In practice, therefore, the resin solutions or suspensions to be applied are prepared immediately before use and have to be applied relatively quickly thereafter.

The problem addressed by the present invention was to find a way of substantially improving the stability in storage of aqueous resin preparations of the type in question based on melamine- and/or urea-formaldehyde resins. This was to be possible even when the active substance contents of the aqueous preparations were, i LLlI i 0' 3 desirably, relatively high at more than 50% b\ weight, for example in the range from about 60 to 75% by weight.

Essentially, the invention is based on the observation that, by using limited quantities of a selected synthetic zeolite compound, sodium zeolite A and also, to a lesser extent, the hydroxysodalite derived therefrom, it is possible to achieve the desired stability in storage of the aqueous resin preparations so that they remain stable in storage for periods of a few months at room temperature.

According to a first embodiment of the present invention there is provided an aqueous preparation of acid-catalyzed melamine resins and/or urea-formaldehyde resins suitable for use in the stabilization of rock and/or plugging of cavities, characterized in that, to increase their usefulness and particularly to extend their storability, the aqueous preparation further comprises zeolite NaA and/or hydroxysodalite.

According to a second embodiment of the present invention there is provided a process for stabilizing rock, for example in tunnel construction and mining, by injection of aqueous preparations of melamine resin and/or ureaformaldehyde condensates together with an acidic catalyst, characterized in that the aqueous preparations further comprise zeolite NaA and/or 20 hydroxysodalite suspended together with the melamine resin and/or ureaformaldehyde condensates and are mixed with the acidic catalyst before injection.

According to a third embodiment of the present invention there is provided a method of improving the usefulness and extending the storage life 25 of aqueous preparations of acid-catalyzed melamine resins and/or ureaformaldehyde condensates said method comprising adding zeolite NaA and/or hydroxysodalite to said aqueous preparations.

Finally, in an.ther embodiment, the invention relates to the use of zeolite NaA and/or hydroxysodalite in aqueous preparations of acid-catalyzed melamine resins and/or urea-formaldehyde condensates for improving their usefulness and extending their storage life.

The content of curable resin active substance in aqueous preparations of the type in question is typically in the range from about 50 to 80% by weight and preferably A, KXW/GSA/163312.doo L j D 8609 4 in the range from about 55 to 75% by weight. It has been found that even the addition of small quantities of the finely divided mineral stabilizers mentioned and, in particular, the addition of very small quantities of zeolite NaA is sufficient to produce a surprisingly effective extension of storage life. Storage life is determined by comparing the viscosity of the material before and after ageing.

More particularly, it has been found that even quantitles of only about 0.1% by weight and, preferably, quantities of at least about 0.5% by weight of zeolite NaA, based in each case on the active subst'nce content of the aqueous resin preparation, are sufficient to produce the desired increase in storage life. Particularly suitable additions of the mineral stabilizers mentioned are in the range from about 0.1 to 20% by weight and preferably in the range from about 0.5 to 15% by weight. Additions of from about 1 to 10% by weight are entirely sufficient for ensuring a storage life at room temperature of, for example, 2 to 3 months.

Another embodiment of the invention is characterized in that urea is additionally added to the aqueous resin preparations and is dissolved in the aqueous phase. It has been found in this regard that the unwanted emission of formaldehyde can be suppressed by this measure to below the detection limit of formaldehyde. This is understandably a considerable advantage where these injection solutions are applied in tunnel construction for example. According to the invention, the preferred urea contents of the injection slolution are from about 10 to 40% by weight and, more preferably, from about 15 to 25% by weight, again based on the active substance content of the aqueous solution of reactive resins.

The resin solution is cured in known manner by acidic catalysis, more particularly by the addition of mineral INTERNATIONALER RECHERCHENBERICHT Internationales Aktenzechen PCT/EP 90/00353 lordF~P u~IM4J btmhe~_~s~~aIo~yioqnun isalgbn Lie K -AUSSIFNATION DES3 APIMELDLINGSGSEiG.CNI TADS (bl mehraren Klasoltlkationssymnbolo~n sind aile aniugsbeniS I Nach djer Intenaiionalen Patentklassiflkadon (IPC) oder nach der natinnalan itip

I

i D 8609 acids. Although, basically, any mineral acid is suitable for initiating the curing reaction, it is often advisable to use phosphorous acid. It is known that this acid has the advantage that it does not attack iron components to any real extent so that no hydrogen is formed.

The mineral acids are preferably added to and mixed with the resin-containing injection solutions before application in the form of aqueous solutions. It can be particularly useful in this regard initially to mix the mineral acids into aqueous electrolyte salt solutions and to mix the acids diluted in this form with the resin preparation to be injected. Suitable electrolyte salts are, in particular, water-soluble salts of the alkali and/or alkaline-earth metal group, particular significance being attributed to the salts of sodium, calcium and/or magnesium. Readily water-soluble salts of this class, particularly the chlorides, but even water-soluble sulfates, are suitable representatives of these electrolyte salts. Examples are sodium chloride and calcium chloride.

The mineral acids are used in particular in a concentration of from about 10 to 30% by weight in the electrolyte salt solution which in turn contains the electrolyte salts in quantities of from about 10 to 40% by weight. The quantity of mineral acid used for curing, based on resin active substance, is in the usual range, for example from about 1 to 15% by weight.

The following Examples, in the form of comparison tests, demonstrate the stabilizing effect of adding the finely divided mineral components, particularly zeolite NaA, in accordance with the invention. Zeolite NaA itself and its production are described in detail in the prior art, cf. for example the basic US-PS 2,882,243 (Milton) and the book by Donald W. Breck entitled "Zeolite Molecular Sieves Structure, Chemistry and Use", John Wiley and Sons, New York/London, 1974, page 133 and also the many 1 i ~I D 8609 6 other references in this book to the typical oxide formula, the crystallographic data and the structural properties.

Today, synthetic crystalline zeolite NaA is used industrially as a sodium tripolyphosphate substitute in detergents and cleaning preparations, particularly laundry detergents.

The detergent qualities of zeolite NaA are particularly suitable for use in accordance with the invention. Hydroxysodalite and its production are also described in the cited literature.

Examp es Example 1 The storage life of an aqueous preparation of a melamine/urea-formaldehyde condensate predominantly containing melamine resin is investigated in a first series of tests. The effect of adding increasing quantities of urea to the melamine resin solution is determined in a first series of experiments. The melamine resin used is a commercial product. The viscosities of the solutions in mPas are measured immediately after addition of the urea to the melamine resin solution in the quartities shown and after storage for a period of 2 months at room temperature.

The following results are obtained: Viscosity in mPas Immediately After 2 months a) Melamine resin solution 10% by weight urea 900 3400 20% by weight urea 625 2900 30% by weight urea 500 2150 40% by weight urea 325 1940 In another series of tests, the melamine resin solution having the stated composition is mixed with 20% by weight urea. Increasing qtantities of zeolite NaA and, in a comparison test, a small quantity of hydroxysodalite are i ijL f- D 8609 7 then added to separate samples of this solution. The percentages by weight shown in Table b) below for the quantities of zeolite and hydroxysodalite added are based on the system as a whole, the figure for urea (20% by weight) being based on the active substance content of the resin solution.

In this case, too, the particular stabilizing effects were determined by measuring the viscosity of the aqueous preparations immediately after their production and after storage for 2 months at room temperature.

Viscosity in mPas Immediately After 2 months a) Melamine resin solution 20% by weight urea 625 2990 0.5% by weight zeolite NaA 650 810 1% by weight zeolite NaA 650 480 10% by weight zeolite NaA 650 400 U.5% by weight hydroxy 650 1600 sodalite Determination of the formaldehyde concentration in the air above the particular material samples shows that, beyond an addition of approximately 10% by weight urea to the 60% melamine resin solution, the free formaldehyde content is reduced to levels below 0.3 ppm.

Example 2 Various quantities of phosphorous acid are added to an aqueous starting material containing 60% by weight melamine resin. The phosphorous acid is used in the form of a solution in aqueous medium, distilled water, tapwater, a sodium chloride solution, saturated sodium chloride solution and a saturated calcium chloride solution being used as the aqueous medium in comparison tests.

D 8609 8 The curing time of the various mixtures is determined in separate tests, comparison tests being carried out at room temperature, at 40°C and at 70°C. The curing time defined as the period of time beyond which the system can no longer be stirred with a spatula in a small-scale test.

A period of 1 hour (1 h) is selected as the upper time limit for the comparatively slow-curing systems. If the curing time is below that limit, it is shown in minutes and seconds The curing times determined in these comparison tests are shown in the following Table.

A41I i c? D 86Q9 conditions resin solution Curing time at RT 400C 70-C in a) Dist. water b) Tapwater c) 159V NaCi solutiu.n d) Sat. NaCi solution e) Sat. CaCi solution 2% acid solution RT 40-C 70-C lh/ lh/11'53" lh/ Ih/8'24" lh/41'20"/13' lh/35'/12' lh/30 29" acid solution RT 400C 700C 45'/11'/4'41" 45'/12'05"/3 '29" 18'/11' 03"/5' 251/10105"/4 1051- 6'40"/5'/2 '/35" +10% acid solution RT 4000 70-C 4'/3 /l111/115611 4 '05 '23 ~15011 3/'/211011/11221 1'411"/1'3211/1 02"1 l'49"/l'2911/l'1711 +14% acid solution RT 40-C 3 '0511/5211 3 '/1'1511/5511 2/'/5511/2911 55",/49" /24"1 1' 08"/45"/3 3"

Claims

1. An aqu!eous preparation of acid-catalyzed melamine resins and/or urea-formaldehyde resins suitable for use in the stabilization of rock and/or plugging of cavities, characterized in that, to increase their usefulness and particularly to extend their storability, the aqueous preparation further comprises zeolite NaA and/or hydroxysodalite.

2. An aqueous preparation as claimed in claim 1, characterized in that the zeolite NaA or hydroxysodalite is in a suspended form in quantities of from about 0.1 to about 20% by weight based on the active substance content of the aqueous preparation.

3. An aqueous preparation as claimed in claim 2, characterized in that the quantities are from about 0.5 to about 15% by weight.

4. An aqueous preparation as claimed in any one of claims 1 to 3, characterized in that the aqueous preparation further comprises urea.

5. An aqueous preparation as claimed in claim 4, characterized in that the urea is present in quantities of from about 10 to about 40% by weight based on the active substance content of the aqueous preparation.

6. An aqueous preparation as claimed in any one of claims 1 to characterized in that the aqueous preparation comprises about 50 to about 8 0% by weight curable melamine resins and/or urea-formaldehyde condensates based on the active substance content.

7, An aqueous preparation as claimed in claim 6, characterized in that the aqueous preparation comprises about 55 to about 75% by weight of curable melamine resins and/or urea-formaldehyde condensates.

8. An aqueous preparation of acid-catalyzed melamine resins and/or urea-formaldehyde resins, substantially as hereinbefore described with reference to any one of the Examples but excluding the Comparative Examples.

9. A process for stabilizing rock, for example in tunnel construction and mining, by injection of aqueous preparations of melamine resin and/or urea-formaldehyde condensates together with an acidic catalyst, characterized in that the aqueous preparations further comprise zeolite NaA and/or hydroxysodalite suspended together with the melamine resin and/or urea- formaldehyde condensates and are mixed with the acidic catalyst before Injection. A process as claimed in claim 9, characterized in that the acidic catalyst is in an aqueous solution.

KXW/CSA/163312.doo -V 11

11. A process as claimed in claim 9 or 10, characterized in that the acidic catalyst is an aqu ous solution of a mineral acid.

12. A process as claimed in claim 9 or 10, characterized in that the acidic catalyst is an aqueous solution of phosphorus acid.

13. A process as claimed in claim 11, characterized in that tne mineral acids are in aqueous electrolyte solutions.

14. A process in claim 13, characterized in that the acid content of the aqueous electrolyte solutions is from about 10 to about 30% by weight.

A process as claimed in claim 13 or 14, characterized in that the lo aqueous electrolyte solution comprises from about 10 to about 40% by weight of dissolved electrolyte salts.

16. A process as claimed in any one of claims 13 to 15, characterized in that the electrolyte salts are alkali and/or 31kaline earth salts.

17. A process as claimed in claim 16, characterized in that the alkali and/or alkaline earth salts are chlorides of sodium, calcium and/or magnesium.

18. A method of improving the usefulness and extending the storage life of aqueous preparations of acid-catalyzed melamine resins and/or urea- formaldehyde condensates said method comprising adding zeolite NaA and/or hydroxysodalite to the aqueous preparations.

19. The method as claimed in claim 18, characterized in that the aqueous preparation further comprises dissolved urea. A method of improving the usefulness and extending the storage Slife of aqueous preparations of acid-catalyzed melamine resins and/or urea- formaldehyde condensates, substantially as hereinbefore described with 25 reference to the Examples but excluding the Comparative Example. DATED this TWENTY-EIGHTH day of APRIL 1992 Kommanditgesellschaft auf Aktien,. E. Epple Co., GmbH Patent Attorneys for the Applicants SPRUSON FERGUSON o KXW/GSA/16331 2doo 0 1.Temto scamdi li 8 hrceie nta h i; _I D 8609 Abstract The invention relates to aqueous preparations of acid- catalyzed melamine resins and/or urea-formaldehyde conden- sates which contain an addition of zeolite NaA and/or hydroxysodalite to increase their usefulness. The prepara- tions in question are particularly suitable for use in the stabilization of rock and/or plugging of cavities, for example in tunneling and mining. Accordingly, the inven- tion also relates to a process for stabilizing rock, for example in tunneling and mining, by injection of corre- sponding preparations together with an acidic catalyst. S.I I i~n j~i i .~b INTERNATIONAL SEARCH REPORT International Application No PCT/EP 90/00353 I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, Indicrte all) According to International Patent Classification (IPC) or to both National Classification and IPC Int.Cl. 5 E 21 B 33/138, C 09 K 17/00, C 08 K 3/34 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classificatio, Symbols Int.C1. C 09 K, E 21 B, C 08 K, C 08 J Documentation Searche' other than Minimum Documentation to the Extent that such Documents are Included in the Fields Searched III. DOCUMENTS CONSIDERED TO BE RELEVANT9 Category Citation of Document, 11 with Indication, where appropriate, of the relevant passages 12 Relevant to Claim No, 13 A DE, A, 1153698 (PEUTE-CHEMIE AG) 1,6 September 1963 see claim 1 (cited in the application) A US, A, 4114382 KUBENS) 1,9 19 September 1978 see claim 1; column 4, lines 4-7 A GB, A, 1106301 FARKAS) 13 March 1968 see claims 1-3; page 1, line 57 page 2, line 31 A US, A, 3237691 KOCH) 1,7-8 1 March 1966 see claims 1-16 SSpecial categories of cited documents: 10 late ,ocument published after the International filing date document defining the general state of the art which is ot o' t,(orlty date and not In conflict with the application but consideird be of particular relevance c l ad to understand the principle or theory underlying the invention earr document but published on or after the international doc.ment of particular relevance; the claimed Invention fillnj date I cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or Involve an Inventive step which Is cited to establish the publication date of another Y" document of particular relevance;' the claimed invention citation or other special reason la speed) cannot be considered to Involve an Inventive step when the 0" document roferrinp to an oral disclosure, use, exhibition or document is combined with one or more other such docu. other means nients, such combination being obvious to a person skilled document published prior to the International filing date but in the art. litter Than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this Internationd Search Report 6 June 1990 (06,06,90) 2 July 1990 (02.07.90) International Searching Authorit/ Signature of Authorized Ofi/.er European Patent Office Form PCT/ISA/210 (second sheet) (January 1985) Y -e I? 4 1~ -bowm.Soh Apoeegti No. PCT/EP 90/00353 Il. DOCUMENTS CONUUIUI TO 1 RLEVANT XOINlUUD FROM THE SaCOD &nmEET) CaI.ory canon al DoommWS. wm sommon. rwng =*cams. of Usrcsrm e mF kc o 081tg No US, A, 4473119 FALK) September 1984 see claims 1,5; column 4, lines 1,10 Form PCTIISII (owm mhneO IwivnY IB) ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 9000353 SA 34883 This avnex lists the patent family members relating to the patent docu,,nents: rket in the above-mentioned international search report. The members are as contained in the European Patent Office EDP ie on 21106/90 The European Patent Office is in no way liable for thcese particulars wvhich are nic'ely given for the purpose of information. Patent document Publication Patent family Pblication cited in search report date member(s) 7-udate DE-A- 1153698 None US-A- 4114382 19-09-78 DE-A- 2436029 05-02-76 AU-A- 8337475 27-01L-77 BE-A- 831668 17-11-75 CA-A- 1074092 25-03-80 FR-A,B 2279891 20-02-76 GB-A- 14-50306 22-09-76 JP-A- 51039912 03-04-76 GB-A- 1106301 None US-A- 3237691 None US-A- 4473119 25-09-84 None A' For more details about Ibis annex -see Official Journal of the European Patent Office, No. 12/82. INTERNATIONALER RECHERCHENBERICHT internationales Aktenzeichen PCT/EP 90 /00353 1. KLASSIFIKATION DES AMMELOUNGSGEGENSTANDS (bat mehreren Klassifikaxionisvnibaiqn sind all. anzugeben) 6 Nach der internatonalen Patenlk lassifikatio n I IPC) odier nach der nationalen Kiassifikation und cder IPC Int.CI 5 E 21 B 33/138, C 09 K 17/00, C 08 K 3/34 11. RECHERCHIERTE SACHGEBIETE Recherchierter MindestprufStoff 7 Klassifikationssvstem Klassifikationssymbtile Int.C 5 C 09 K, E 21 B, C 08 K, C 08 J Recherchierte nicht zumn MiridestprUfstoff gehorende Verdffentlichungen, soweit diese unter die recherchierten Sachgebiete fallen 8 III.EINSCHLAGIGE VEROFF!ENTLICHUNGEN 9 -Art* Kennzeichnung der Veroffentlichungll,soweit erfarderlich unter Angabe der mal~gebllchen Teile1 2 Betr. Anspruch Nr,1 3 A DE, A, 1153698 (PEUTE-CHEMIE AG) 1,6 September 1963 siehe Patentanspruch 1 (in der Annmeldung erw~hnt) A US, A! 4114382 KUBENS) 1,9 19. September 3.978 siehe Patentanspruch 1; Spalte 4, Zeilen 4-7 A GB, A, 1106301 FARKAS) 13. Mar? 19,1'8 siehe Patei,.anspriiche 1-3; Seite 1, Zeile 57 Seite 2, Zeile 31 *Bescridere Kategorien von angegebenen Veroffentlichungen Veroffentlichung, die den ailgemneinen Stand der Technik Spatere Veriffentllchung, die nach demn internationalen An, definiert, aber nicht als besanders bedieutsamn anzusehen Ist meldedlatumn oder demn Priaritaitsdatumn verbffc -tit:h wo'-z" 1jers Ooumenist und mit der Anmeldung nicht kollidiert, sondern nur zumn "E ltees okuen, das jedocir erst am oder nach demn interna- Verstandnis des der Erfindung zugrundellegenden Prinzips tianalen Anmeldedatumn veroffentiicht warden Ist oder der ihr zugrundeliegenden Theorie angegeben 1st Veroffentlichung, die geeignet is%, eine., Priaritatsanspruch Vero~ffentlichung von besonderer Bedeutung; die beanspruch. zweifelhaft erscheinen zu laizen, oder durch die das Veraf- eEfnugkn ih l euoe u ridrthrTtg fentlichungsdatumn elner anderen im Recherchenberich e kto eruend beanncht ne e den afefnershrTtg nariten 'Verdffentlichung belegt werden sail cider die aus eierni anderen besonderen Grund angeeben ist IWe ausgefi~hrt) Veroffentlichung von besonderer Bedleutung; die beanspruch. er~fenichngdie ichaufsin mindllhe ffebarng, tt Erflndlung sann nlcht als auf erfinderitcher Tatigkeit be, "0 ere Bentzcu ng, ie sihausselner nderce Mailnbahn ruhend betrachtet werden, wenn die Veroffentlichung mit bie letzu eieAstlugoe neeMlnhe lner oder mehreren anderen Veroffentlichungen dieset' Kate, beziehtgonie in Verbindung gebracht wird und diese Verbindlung fUr Veroffentlichung, die vorn demn internatianalen Anmeldedla. eiren Fachmann riaheliegend ist turn, eber nach demn bc:nspruchten Prloritatsdlatumn verdffont. ~VrfetihndeMtle esle aetaii t licht worden istVVrfetihndeMlgie esle aetaii IV. BESCHEINIGUNG Datum des Abschlusses der internatlonalen Recherche Absendledatumn des internationalen Recherchenberlchts 6. Juni 1990 2. ir Rn Internationale Recherchenbehorde Unterschritt des beva!Irnachtigtoih Bedlie isteten Europaisches Patmnuamt ~E~ V K I Formilatt PCT/ISA/21 0 (Blatt 2) (Januar 1985) I Interntionals A; :eichnPCT/EP 90/00353 2- III.EINSCHLAGIGE VEROFFENTLICHUNGEN (Fortsectung van Blatt 2) Art Kennzeichnung der Verotfentlichung. sawelt erforderlich unter Angabe der fnaageblichen Talle Betr. Anspruch Nr. US, A, 3237691 KOCH) 1. 'Mdrz 1966 siehe Patentanspriiche 1-16 US, A, 4473119 FALK) September 1984 siehe Patentansprtiche 1, 5; Spalte 4, Zeilen 1,7-8 1,10 I. Forrnblatt PCTj'ISAI210 IMuaatbogan) (Jmnuar 1985) ANHANG ZUM INTERNATIONALEN RECHERCHENBERICHT OBER DIE INTERNATIONALE PATENTANMELDUNG NR. EP 9000353 SA 34883 In diesem Anhang sind die '4itglieder der Patentfamilien der im obiengenannten internationaten Recherchenbericht angefdhrtzn Patentdokumente angegeben. Die Angaben fiber die Familienmitglieder entsparechen dem Stand der Datei des Europikf'n ?/Atentamts am 22/06/90 Diese Angaben dienen nur zur Unterriebtung und erfolgen ohne Gewahr. Im Recherchenbericht T Datum der Mitglied(er) der Datum der angefuhrtes Patentdokument Verbffentlichung Patentfamilie -T Verbffentlichung DE-A- 1153698 Keine US-A- 4114382 19-09-78 DE-'A- 2436029 05-02-76 AU-A- 8337475 27-01-77 BE-A- 831668 17-11-75 CA-A- 1074092 25-03-80 FR-A,B 2279891 20-02-76 GB-A-- 1450306 22-09-76 ~JP-A- 51039912 03-04-76 GB-A- 1106301 Keirie US-A- 3237691 Ke in e US-A- 4473119 25-09-84 Keine 0jir tihere Einzelbeiten zu diesem Anhang :siehe Amtsblatt des Europ~ischell Patentamts, Nr.12/82